CN103890986A - Thermoelectric conversion element and process for producing same - Google Patents
Thermoelectric conversion element and process for producing same Download PDFInfo
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- CN103890986A CN103890986A CN201280051044.6A CN201280051044A CN103890986A CN 103890986 A CN103890986 A CN 103890986A CN 201280051044 A CN201280051044 A CN 201280051044A CN 103890986 A CN103890986 A CN 103890986A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C12/00—Alloys based on antimony or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/12—Anodising more than once, e.g. in different baths
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/16—Pretreatment, e.g. desmutting
Abstract
A thermoelectric conversion element which comprises a substrate having a porous anodized aluminum coating film and, deposited on the substrate, a thermoelectric conversion layer that comprises an inorganic oxide semiconductor or an element having a melting point of 300 DEG C or higher as a main component and that has a structure having voids; and a process for producing the thermoelectric conversion element.
Description
Technical field
The present invention relates to thermoelectric conversion element and manufacture method thereof.
Background technology
The thermo-electric converting material that heat energy and electric energy can be changed is mutually used in the thermoelectric conversion element such as thermoelectric generation elements, Peltier element.The thermoelectric power generation of having applied thermo-electric converting material, thermoelectric conversion element can directly become electric power by thermal power transfer, has advantages such as not needing movable part, is used to the wrist-watch of working or for isolated area in power supply, space power supply etc. under body temperature.
Proposed various metal materials as thermo-electric converting material, for example, the film that has bibliographical information to be made up of the compound of indium oxide and palladium demonstrates thermoelectricity transfer characteristic (non-patent literature 1).In addition, the film that has bibliographical information zinc antimony film forming to be obtained on quartz base plate by sputtering method demonstrates thermoelectricity transfer characteristic (non-patent literature 2).
In order to improve thermoelectricity conversion performance, attempting exploring the improvement of new thermo-electric converting material and element.Thermoelectricity conversion performance changes according to the Seebeck coefficient of thermo-electric converting material, conductivity and conductive coefficient, and Seebeck coefficient and conductivity are larger, the less thermoelectricity of conductive coefficient conversion performance is higher.
In non-patent literature 3, reported following content: by anodic oxidation aluminium base by flash method by BiSbTe material filming, can obtain the film of Porous shape; And this film conductive coefficient compared with the film forming with same metal material on quartz base plate reduces.But, conductivity and Seebeck coefficient reduction compared with having used the situation of quartz base plate.
Prior art document
Non-patent literature
Non-patent literature 1:O.T.Gregory et al., " Thermoelectric power factor of In
2o
3: Pd nanocomposite films ", Applied Physics Letters, Vol.99,013107,2011 year
Non-patent literature 2:K.Ito et al., " Low Thermal Conductivity and Related Thermoelectric Properties of Zn
4sb
3and CoSb
3thin Films ", Mat.Res.Soc.Symp.Proc., Vol.793,, S5.1.1 in 2004
Non-patent literature 3:M.Kashiwagi et al., " Enhanced figure of merit of a porous thin film of bismuth antimony telluride ", Applied Physics Letters, Vol.98,023114,2011 year
Summary of the invention
The problem that invention will solve
Problem of the present invention is to provide possesses the excellent thermoelectric conversion element of thermoelectricity conversion performance and the manufacture method of this element.
For the scheme of dealing with problems
In view of above-mentioned problem, in order to improve the performance of thermoelectric conversion element, the inventor conducts in-depth research.Found that: if the material filming being formed by inorganic oxide semiconductor or dystectic element is formed to thermoelectric conversion layer on the aluminium base with Porous anodic oxide coating, in thermoelectric conversion layer, form gap structure, conductive coefficient reduces; And conductivity and Seebeck coefficient also very excellent.The present invention completes based on this opinion.
,, according to the present invention, provide following technical proposals:
<1> thermoelectric conversion element, on substrate upper strata, long-pending thermoelectric conversion layer forms for it, described substrate has the Porous anodic oxide coating of aluminium, and it is that 300 DEG C of above elements are as main component and have gap structure that described thermoelectric conversion layer contains inorganic oxide semiconductor or fusing point.
The thermoelectric conversion element of <2> as described in <1> item, wherein, described inorganic oxide semiconductor contains indium.
The thermoelectric conversion element of <3> as described in <1> item, wherein, described inorganic oxide semiconductor is for selecting free In
2o
3, SnO
2, ZnO, SrTiO
3, WO
3, MoO
3, In
2o
3-SnO
2, fluorine-doped tin oxide, antimony-doped tin oxide, stibium-doped zinc oxide, Ga-doped zinc oxide, In
2o
3-ZnO and gallium doping In
2o
3material in the group of-ZnO composition.
The thermoelectric conversion element that <4> states as <1> item, wherein, it is that 330 DEG C of above elements are as main component that described thermoelectric conversion layer contains fusing point.
The thermoelectric conversion element of <5> as described in <1> or <4> item, wherein, described thermoelectric conversion layer contains selects free Zn
4sb
3, CoSb
3, MnSi
1.
75, Mg
2si, SiGe and FeSi
2alloy in the group of composition is as main component.
The thermoelectric conversion element of <6> as described in any one in <1>～<5>, wherein, the aperture opening ratio of described Porous anodic oxide coating meets following mathematical expression (I).
Mathematical expression (I) aperture opening ratio=φ/P>0.5
(in formula, φ represents average pore size, and P represents average span.)
The thermoelectric conversion element of <7> as described in any one in <1>～<6>, wherein, the average pore size in the hole of described Porous anodic oxide coating is more than 60nm.
The manufacture method of a <8> thermoelectric conversion element, described manufacture method comprises following operation: on substrate, thermo-electric converting material film forming is formed to thermoelectric conversion layer, described substrate has the Porous anodic oxide coating of aluminium, and described thermo-electric converting material contains inorganic oxide semiconductor or fusing point is that 300 DEG C of above elements are as main component.
The manufacture method of the thermoelectric conversion element of <9> as described in <8> item, wherein, described manufacture method comprises following operation: on substrate, thermo-electric converting material film forming is formed to thermoelectric conversion layer, described substrate has the Porous anodic oxide coating of aluminium, and it is that 300 DEG C of above elements are as main component that described thermo-electric converting material contains fusing point; And this thermoelectric conversion layer is carried out to annealing in process.
The manufacture method of the thermoelectric conversion element of <10> as described in <8> item, wherein, described manufacture method comprises following operation: on substrate, be, under more than 150 DEG C conditions, thermo-electric converting material film forming is formed to thermoelectric conversion layer at substrate temperature, described substrate has the Porous anodic oxide coating of aluminium, and it is that 300 DEG C of above elements are as main component that described thermo-electric converting material contains fusing point.
The manufacture method of the thermoelectric conversion element of <11> as described in any one in <8>～<10>, wherein, described manufacture method comprises following operation: aluminium sheet is carried out to anodic oxidation with oxalic acid, obtain having the substrate of described Porous anodic oxide coating.
The manufacture method of the thermoelectric conversion element of <12> as described in any one in <8>～<11>, wherein, described film forming is undertaken by vapor coating method.
The effect of invention
Thermoelectric conversion element of the present invention demonstrates excellent thermoelectricity conversion performance, can be suitable for various thermoelectric power generation article.In addition, according to the manufacture method of thermoelectric conversion element of the present invention, can obtain possessing the thermoelectric conversion element of excellent thermoelectricity conversion performance.
Suitably with reference to accompanying drawing, can be by further above-mentioned and further feature and advantage clearly of the present invention of following record content.
Brief description of the drawings
Fig. 1 is the schematic diagram that an example of thermoelectric conversion element of the present invention is shown.
Fig. 2 is the partial cross section figure of anodizing of aluminium epithelium.
Fig. 3 is the figure that is shown schematically in the process of film forming thermo-electric converting material on anodic oxide coating.
Embodiment
On substrate upper strata, long-pending thermoelectric conversion layer forms thermoelectric conversion element of the present invention, and described substrate has the Porous anodic oxide coating of aluminium, and described thermoelectric conversion layer contains inorganic oxide semiconductor or fusing point is that 300 DEG C of above elements are as main component.By the long-pending thermoelectric conversion layer in the porous layer upper strata at anodised aluminium epithelium, thereby in layer, formed gap structure, the conductive coefficient that can realize layer reduces.In addition,, by using inorganic oxide semiconductor or dystectic element as the main component of thermoelectric conversion layer, can also improve conductivity and Seebeck coefficient.
Thermoelectric conversion element utilizes Seebeck effect to carry out thermoelectricity conversion, as the index that represents its thermoelectricity conversion performance, and the performance index Z that has used following formula (A) to represent.
Formula (A): Z=S
2σ/κ
S (V/K): thermo-electromotive force (Seebeck coefficient)
σ (S/m): conductivity
κ (W/mK): conductive coefficient
In formula, S represents Seebeck coefficient, and σ represents conductivity, and κ represents conductive coefficient.Seebeck coefficient is the thermo-electromotive force of every 1K absolute temperature.
In order to improve the thermoelectricity conversion performance of element, require absolute value and the conductivityσ of the Seebeck coefficient S that increases thermoelectric conversion layer, thermo-electric converting material, reduce conductive coefficient κ.
The thermoelectric conversion layer of thermoelectric conversion element of the present invention has gap structure, and conductive coefficient reduces thus.In general, if there is the conductive coefficient reductions such as pore in layer, resistivity also rises on the other hand, thereby conductivity reduces.But, in the present invention by using inorganic oxide semiconductor or there is the element of specific fusing point as the material of thermoelectric conversion layer, thereby can under the state that maintains gap structure, obtain all excellent thermoelectric conversion layer of conductivity and Seebeck coefficient.Thermoelectric conversion element of the present invention can be brought into play excellent thermoelectricity conversion performance by the cooperative effect of these conductive coefficients, conductivity and Seebeck coefficient.
In addition, there is the substrate of the Porous anodic oxide coating of aluminium by use, can obtain the element of the adaptation excellence of substrate and thermoelectric conversion layer.Adaptation by substrate and thermoelectric conversion layer improves, and can suppress the warpage of substrate or peel off the crackle causing, thereby can bring into play better thermoelectricity conversion performance.
Be illustrated in Fig. 1 by one of thermoelectric conversion element of the present invention.Thermoelectric conversion element 1 possesses aluminium base 2, be formed at the surperficial anodic oxide coating 3 of this substrate and the thermoelectric conversion layer 4 of film forming on this anodic oxide coating.Except substrate and thermoelectric conversion layer, thermoelectric conversion element of the present invention can also have the electrode of substrate and thermoelectric conversion layer electrical connection.As shown in Figure 2, substrate has the Porous anodic oxide coating 13 of aluminium.In alumilite process epithelium 13, being formed with cross sectional shape is nearly straight tube shape and the micropore 15 with honeycomb arrangement.
Below, suitably, with reference to these accompanying drawings, the present invention is described in detail.
[substrate]
As long as the substrate of thermoelectric conversion element of the present invention has the Porous anodic oxide coating of aluminium.Such substrate can form anodic oxide coating at substrate surface by aluminium base is implemented to anodized and obtain.Anodizing of aluminium epithelium is made up of the barrier layer as basalis and porous layer formed thereon.Porous layer has regularly arranged multiple pores (micropore) (Fig. 2).Thermoelectric conversion element of the present invention on this porous layer by thermoelectric conversion layer film forming.
The anodizing of aluminium epithelium forming by anodized himself is can be independently, therefore after anodized, can remove as the aluminium sheet of substrate and the substrate as element by epithelium part only, surface can also be formed with to the aluminium sheet of anodic oxide coating as substrate.
Below, the manufacture method of the Porous anodic oxide coating to aluminium describes.
< aluminium base >
Aluminium base is not particularly limited, can enumerates pure aluminum plate; Using aluminium as main component and the alloy sheets that comprises micro-different elements; The substrate that aluminium (for example, recycled materials) evaporation raffinal to low-purity forms; On the surface of silicon chip, quartz, glass etc. by method coatings such as evaporation, sputters the substrate of raffinal; Lamination the resin substrate of aluminium; Etc..
Aluminium base is preferably implemented the high aluminium base of purity of the surperficial aluminium of anodized.Specifically, more than aluminium purity is preferably 99.5 quality %, more preferably more than 99.9 quality %, more preferably more than 99.99 quality %.If aluminium purity is in above-mentioned scope, the micropore (pore) forming on the surface of alumilite process epithelium to be arranged with sequence good, therefore preferably.
For aluminium base, can before carrying out anodized, carry out pre-treatment.For example, the order of arranging in order to improve hole, preferably heat-treats in advance.In addition, preferably implement in advance ungrease treatment, minute surface fine finishining processing on the surface of the anodized of implementing aluminium base.
< heat treatment >
Heat treatment is preferably carried out about 30 seconds～2 minutes at 200 DEG C～350 DEG C.Specifically, can enumerate and aluminium base be put into method that heating furnace heats etc.By implementing such heat treatment, the order of the arrangement of the micropore forming on the surface of anodic oxide coating improves.
Aluminium base after above-mentioned heat treatment is preferably promptly cooling.As cooling means, can enumerate method substrate directly being dropped in water etc. etc.
< ungrease treatment >
Ungrease treatment is to use acid, alkali, organic solvent etc. that the organic principle such as dust, grease, resin etc. that is attached to aluminium base surface is dissolved and the processing of removal.Its generation for the defect that the organic principle preventing in the each processing of aftermentioned causes is carried out.
As the method for ungrease treatment, can enumerate: the method (organic solvent method) that makes at normal temperatures various alcohol (methyl alcohol etc.), various ketone (methyl ethyl ketone etc.), petroleum benzin, volatilization wet goods organic solvent and aluminium base Surface Contact; In normal temperature～80, DEG C left and right makes the liquid and the aluminium base Surface Contact that contain the surfactant such as soap, neutral detergent, the method for washing afterwards (surfactant method); Making concentration in DEG C left and right, normal temperature～70 is the aqueous sulfuric acid of 10g/L～200g/L and aluminium base Surface Contact about 30 seconds～80 seconds, the method for washing afterwards; Making at normal temperatures concentration is the sodium hydrate aqueous solution of 5g/L～20g/L and aluminium base Surface Contact about 30 seconds, make simultaneously aluminium base surface for negative electrode circulating current density be 1A/dm
2～10A/dm
2direct current carry out electrolysis, the method that the aqueous solution of nitric acid that exposure concentration is 100g/L～500g/L afterwards neutralizes; Make at normal temperatures various anodized electrolyte contact with metallic substrate surfaces, make simultaneously aluminium base surface for negative electrode circulating current density be 1A/dm
2～10A/dm
2direct current or the circulation alternating current method of carrying out electrolysis; At 40 DEG C～50 DEG C, making concentration is the alkaline aqueous solution of 10g/L～200g/L and aluminium base Surface Contact about 15 seconds～60 seconds, the method that the aqueous solution of nitric acid that exposure concentration is 100g/L～500g/L afterwards neutralizes; In normal temperature～50, DEG C left and right makes the emulsion contact aluminium base surface that mixed surfactant, water etc. form in light oil, lam-oil etc., the method for washing afterwards (emulsion degreasing method); In normal temperature～50, DEG C left and right makes the mixed liquor of sodium carbonate, phosphoric acid salt, surfactant etc. and aluminium base Surface Contact about 30 seconds～180 seconds, the method (phosphate method) of washing afterwards; Etc..
Among these, due to the dissolving that can remove the lubricant component on aluminium base surface and substantially not produce aluminium, thereby preferably organic solvent method, surfactant method, emulsion degreasing method, phosphate method.
In addition, ungrease treatment can be carried out with common degreasing agent.For example, can be by carrying out with commercially available various degreasing agents with the method for regulation.
> is processed in the fine finishining of < minute surface
Minute surface fine finishining processing for example, is carried out for rolling striped concavo-convex, that produce when the rolling of aluminium base of eliminating aluminium base surface etc.
Method to minute surface fine finishining processing is not particularly limited, for example, can use the usual ways such as mechanical lapping, chemical grinding, electrolytic polishing.
As mechanical lapping, for example, can enumerate the method for grinding with various commercially available abrasive cloths, the method that commercially available various grinding agents (such as diamond, aluminium oxide) and polishing wheel are combined etc.Specifically, using grinding agent in the situation that, can suitablely exemplify by used grinding agent through time change to by coarse granule the method that fine particle carries out.
As chemical grinding, for example can enumerate " aluminium handbook ", the 6th edition, (society) Japanese aluminium association compiles, calendar year 2001, the whole bag of tricks etc. of recording in p.164-165.
In addition, can suitablely enumerate phosphoric acid-nitrate method, Alupol I method, Alupol V method, Alcoa R5 method, H
3pO
4-CH
3cOOH-Cu method, H
3pO
4-HNO
3-CH
3cOOH method.Wherein, preferably phosphoric acid-nitrate method, H
3pO
4-CH
3cOOH-Cu method, H
3pO
4-HNO
3-CH
3cOOH method.
As electrolytic polishing, for example, can suitablely enumerate " aluminium handbook ", the 6th edition, (society) Japanese aluminium association compiles, calendar year 2001, the p.164-165 middle the whole bag of tricks of recording; The method of recording in No. 2708655 specification of United States Patent (USP); " practice sufacing ", vol.33, No.3,, the p.32-38 middle method of recording in 1986; Etc..
These methods can be used by proper combination.For example, preferably implement by grinding agent through time change to fine grain mechanical lapping by coarse granule, implement afterwards electrolytic polishing.
< anodized >
The anodized of aluminium base can be used usual way.For example, can use from ordering method (own Regulations Theization method).Refer to following method from ordering method: utilize the regularly arranged character of micropore forming on anodic oxide coating, remove the reason that upsets regular arrangement, improve thus order.Specifically, use highly purified aluminium base, be suitable for electrolyte kind voltage, for example, form anodic oxide coating with long-time (several hours to tens hours) low speed.In the method, aperture depends on voltage, therefore can obtain in a way desired aperture by controlling voltage.
In the present invention, anodized is preferably undertaken by following anodized (a-1), more preferably on the basis of anodized (a-1), carries out in the lump demoulding processing (a-2), anodized (a-3) again.Anodized (a-1), demoulding processing (a-2), anodized (a-3) can be carried out respectively more than twice again.For example, preferably repeat successively more than twice anodized (a-1) and demoulding processing (a-2), then carry out again anodized (a-3).In addition, also can carry out afterwards demoulding processing (a-2) in anodized (a-3) again.
In the time of the above-mentioned treatment process repeating more than twice, the treatment conditions in each operation respectively can be identical, also can be different.
< anodized (a-1) >
Anodized is following processing: for example, in electrolyte solution (solution that acid concentration is 0.01mol/L～5mol/L), carry out electrolysis using aluminium base as anode, substrate surface is oxidized, forms the Porous epithelium of aluminium oxide on surface.
Electrolyte solution is preferably acid solution, more preferably sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzene sulfonic acid, amidosulfonic acid, glycolic, tartaric acid, malic acid, citric acid etc., more preferably sulfuric acid, phosphoric acid, oxalic acid, be particularly preferably oxalic acid.These acid can be used separately or be used in combination of two or more.
The aperture of the micropore forming because of the kind of used acid solution different.In the present invention, more than the average pore size of micropore is preferably 60nm, in order to obtain such aperture, preferably use oxalic acid as electrolyte solution.
Anodized condition, because used electrolyte changes, cannot treat different things as the same, and in general preferably concentration of electrolyte is that 0.01mol/L～5mol/L, liquid temperature are that-10 DEG C～30 DEG C, current density are 0.01A/dm
2～20A/dm
2, voltage is that 3V～300V, electrolysis time are 0.5 hour～30 hours, more preferably concentration of electrolyte is that 0.05mol/L～3mol/L, liquid temperature are that-5 DEG C～25 DEG C, current density are 0.05A/dm
2～15A/dm
2, voltage is that 5V～250V, electrolysis time are 1 hour～25 hours, further preferably concentration of electrolyte is that 0.1mol/L～1mol/L, liquid temperature are that 0 DEG C～20 DEG C, current density are 0.1A/dm
2～10A/dm
2, voltage is that 10V～200V, electrolysis time are 2 hours～20 hours.
Mean flow rate while carrying out anodized is preferably 0.5m/min～20.0m/min, more preferably 1.0m/min～15.0m/min, more preferably 2.0m/min～10.0m/min.Carry out anodized by the flow velocity with above-mentioned scope, can form evenly and have the micropore of high order.
In addition, the method that makes electrolyte flow is not particularly limited, for example, utilizes the method having used such as the general agitating device of blender.Particularly, can show and control the such blender of mixing speed with numeral if utilize, can control mean flow rate, therefore preferably.As such agitating device, for example, can enumerate " magnetic stirring apparatus HS-50D (AS ONE manufacture) " etc.
Anodized, except carrying out under constant voltage, can also be used intermittently or change continuously the method for voltage.In this situation, preferably progressively reduce voltage.Thus, can reduce the resistance of anodic oxide coating, in anodic oxide coating, generate fine micropore, therefore preferably.
< demoulding processing (a-2) >
Demoulding processing is to make the anodic oxide coating forming on aluminium base surface by above-mentioned anodized dissolve the processing of removing.During demoulding is processed, aluminium base does not dissolve, and only dissolves the anodic oxide coating being made up of aluminium oxide (aluminium oxide).
Antianode oxide scale film, order is higher more to approach aluminium base, therefore processes by demoulding and temporarily removes anodic oxide coating, makes the bottom of the anodic oxide coating remaining on the surface of aluminium base be exposed to surface, can obtain orderly pit.
Demoulding is processed by making the aluminium base that is formed with anodic oxide coating contact and carry out with alumina dissolution liquid.As long as alumina dissolution liquid is dissolved oxygen aluminium and in fact dissolved aluminum not.
As alumina dissolution liquid, can use acid solution or aqueous slkali, can enumerate the aqueous solution of the acid such as sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid or their mixture; The aqueous solution of the alkali such as NaOH, potassium hydroxide and lithium hydroxide.In addition, can also use and contain the aqueous solution that is selected from least a kind of material in chromium compound, zirconium compound, titanium sub-group compound, lithium salts, cerium salt, magnesium salts, sodium silicofluoride, zinc fluoride, manganese compound, molybdenum compound, magnesium compound, barium compound, halogen simple substance etc.The solution that two or more these solution of mixing can be formed uses as alumina dissolution liquid.
As concrete chromium compound, for example, can enumerate chromium oxide (III), anhydrous chromium (VI) acid etc.
As zirconium compound, for example, can enumerate ammonium zirconium fluoride, zirconium fluoride, zirconium chloride.
As titanium compound, for example, can enumerate titanium oxide, titanium sulfide.
As lithium salts, for example, can enumerate lithium fluoride, lithium chloride.
As cerium salt, for example, can enumerate cerium fluoride, cerium chloride.
As magnesium salts, for example, can enumerate magnesium sulfide.
As manganese compound, for example, can enumerate sodium permanganate, potassium permanganate.
As molybdenum compound, for example, can enumerate sodium molybdate.
As magnesium compound, for example, can enumerate magnesium fluoride pentahydrate.
As barium compound, for example, can enumerate barium monoxide, barium acetate, brium carbonate, barium chlorate, barium chloride, barium fluoride, barium iodide, barium lactate, barium oxalate, barium perchlorate, barium selenate, barium selenite, barium stearate, barium sulfite, barium titanate, barium hydroxide, barium nitrate or their hydrate etc.In above-mentioned barium compound, preferential oxidation barium, barium acetate, brium carbonate, particularly preferably barium monoxide.
As halogen simple substance, for example, can enumerate chlorine, fluorine, bromine.
Wherein, preferably use and contain aqueous acid, as acid, preferably sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid etc.Also can be two or more sour mixture.
More than the acid concentration of aqueous acid is preferably 0.01mol/L, more preferably more than 0.05mol/L, more preferably more than 0.1mol/L.The upper limit is not particularly limited, is generally preferably below 10mol/L, more preferably below 5mol/L, more preferably below 1mol/L.Unwanted high concentration is unfavorable economically, and higher words aluminium base likely can dissolve.
The temperature of alumina dissolution liquid is preferably more than-10 DEG C, more than more preferably-5 DEG C, more preferably more than 0 DEG C.It should be noted that, if use the alumina dissolution liquid of boiling to process, the starting point of ordering can be destroyed, upset, thereby preferably do not seethe with excitement and use.
In the time using aqueous acid as alumina dissolution liquid, the temperature of aqueous acid is preferably 20 DEG C～60 DEG C.
To the aluminium base that is formed with anodic oxide coating is not particularly limited with the method that alumina dissolution liquid contacts, for example, can enumerate infusion process, gunite.Wherein, preferred infusion process.
Infusion process is that the aluminium base that is formed with anodic oxide coating is impregnated into the processing in alumina dissolution liquid.If stir in the time of impregnation process, can carry out without uneven processing, therefore preferably.
The time of impregnation process is preferably more than 10 minutes, more preferably more than 1 hour, more preferably 3 hours above, more than 5 hours.
In addition, the meltage of anodic oxide coating is preferably 0.001 quality %～50 quality % of anodic oxide coating entirety, more preferably 0.005 quality %～30 quality %, more preferably 0.01 quality %～15 quality %.If meltage is in above-mentioned scope, can dissolve the part of the surperficial irregular arrangement of anodic oxide coating, can improve the order of the arrangement of micropore, simultaneously at the remaining anodic oxide coating in the bottom of micropore, can leave the starting point of the anodized of enforcement in anodized (a-3) again.
< is anodized (a-3) > again
Process and remove anodic oxide coating by above-mentioned demoulding, form after orderly pit on the surface of aluminium base, again implement anodized, can form thus the higher anodic oxide coating of the degree of order of micropore.
Anodized can be used usual way again, preferably under the condition identical with above-mentioned anodized (a-1), carries out.
In addition, can also suitablely use: in making direct voltage constant, repeat intermittently the method for opening and closing of electric current; In changing direct voltage intermittently, repeat the method for opening and closing of electric current.According to these methods, in anodic oxide coating, can generate fine micropore, thereby what improve from the viewpoint of the uniformity in aperture is preferred.
If carry out at low temperatures anodized again, the arrangement of micropore becomes in order, and it is even that aperture also becomes.On the other hand, by carry out anodized again at higher temperature, can upset the arrangement of micropore, and can make the deviation in aperture in the scope of regulation.In addition, can also utilize the processing time to control the deviation in aperture.
Recruitment by the thickness of the anodic oxide coating that anodized causes is again preferably 0.1 μ m～100 μ m, more preferably 0.5 μ m～50 μ m.If recruitment, in above-mentioned scope, can further improve the order of the arrangement in hole.
< aluminium Transformatin >
As required, can remove aluminium base from the anodic oxide coating forming on the surface of aluminium base by above-mentioned anodized.The device substrate using in the present invention, needn't be with aluminum portions as long as at least have Porous anodic oxide coating.The removal of aluminium base can utilize usual way to carry out.For example, can enumerate use be difficult to dissolve anodic oxide coating (aluminium oxide) and easily the treatment fluid of dissolved aluminum only dissolve the method for removing aluminium base.
The preferred thickness of anodizing of aluminium epithelium using in the present invention is more than 6 μ m.
In addition, the aperture opening ratio of the porous layer of anodic oxide coating is preferably more than 0.5.Aperture opening ratio is the aperture that calculated by following mathematical expression (I) ratio with respect to span.
Mathematical expression (I) aperture opening ratio=φ/P>0.5
In mathematical expression (I), φ represents the average pore size of the pore (micropore) of porous layer, and P represents average span.The aperture of porous layer refers to the diameter in the hole of peristome, and average pore size φ is its mean value.The span of porous layer refers to the distance between centers of two adjacent peristomes, and average span P is its mean value.
In the present invention, more than the average pore size φ of porous layer is preferably 60nm.In addition, more than average span P is preferably 100nm.
Thermoelectric conversion element of the present invention is on the porous layer of this anodic oxide coating, thermoelectric conversion layer film forming to be formed.In the time of thermoelectric conversion layer film forming, the porous layer of anodic oxide coating can become as the inorganic oxide of the main component of thermoelectric conversion layer or high-melting-point element (thermo-electric converting material) is piled up and the basis (sufficient Games) of lamination.If porous layer is piled up to thermo-electric converting material as basis, in thermoelectric conversion layer, can form the gap structure corresponding with the shape in the size in the aperture of porous layer, span, hole.This gap structure is called to the gap structure of the thermoelectric conversion layer in the present invention.
Fig. 3 is shown schematically in the process of film forming thermo-electric converting material on the porous layer of anodic oxide coating.Fig. 3's is a) schematic diagram on the top (peristome) of the anodic oxide coating before thermo-electric converting material film forming.Anodic oxide coating 23 has plural micropore 25.Thermo-electric converting material 26 pile up at leisure on the surface of anodic oxide coating 23 (Fig. 3 b), and by thermoelectric conversion layer film forming (Fig. 3 c).
It's too late that degree exerts an influence for having of thinking that the meetings such as the position of gap structure of thermoelectric conversion layer and size, shape reduce conductive coefficient.As previously mentioned, the gap structure of thermoelectric conversion layer determines according to the aperture of porous layer, span, hole shape etc. (hereinafter referred to aperture etc.), therefore, by controlling the aperture etc. of porous layer, can regulate the gap structure of thermoelectric conversion layer.By making the aperture opening ratio, aperture of porous layer in above-mentioned preferable range, can more effectively realize the reduction of conductive coefficient.The gap structure of thermoelectric conversion layer preferably its average pore size is 1nm～100nm, more preferably 5nm～60nm.
It is that any one in 300 DEG C of above elements is as main component that the thermoelectric conversion layer of element of the present invention is used inorganic oxide semiconductor or fusing point.
[inorganic oxide]
The inorganic oxide semiconductor using in thermoelectric conversion layer is preferably the inorganic oxide semiconductor that contains indium.In addition, inorganic oxide semiconductor can be the inorganic oxide semiconductor being doped.By using such inorganic oxide semiconductor, can realize the reduction of conductive coefficient and the raising of conductivity and Seebeck coefficient of thermoelectric conversion layer simultaneously.
Inorganic oxide semiconductor as long as more than containing 90 quality % in thermoelectric conversion layer.Preferably this oxide contain 95 quality % above, more preferably contain 98 quality % more than.
As the semi-conductive concrete example of inorganic oxide, can enumerate In
2o
3, SnO
2, ZnO, SrTiO
3, WO
3, MoO
3, In
2o
3-SnO
2(ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), stibium-doped zinc oxide (AZO), Ga-doped zinc oxide (GZO), In
2o
3-ZnO (IZO), gallium doping In
2o
3-ZnO (IGZO) etc.Be preferably In
2o
3-SnO
2(ITO), In
2o
3-ZnO (IZO), gallium doping In
2o
3-ZnO (IGZO).
In addition, the thermoelectric conversion layer using inorganic oxide semiconductor as main component does not preferably contain in fact tellurium (Te) as main component or other composition described later.Tellurium has sublimability, if thereby in conversion layer, comprise tellurium layer composition can change along with the time, therefore not preferred.Specifically, the content of tellurium is preferably below 5 quality % in thermoelectric conversion layer.
[materials with high melting point]
The fusing point using in thermoelectric conversion layer is that 300 DEG C of above preferred fusing points of element are 330 DEG C of above elements.By using dystectic element, can realize the reduction of conductive coefficient and the raising of conductivity and Seebeck coefficient of thermoelectric conversion layer simultaneously.
The fusing point using as main component be 300 DEG C of above elements can be a kind can be also two or more, as long as fusing point is 300 DEG C of above elements in thermoelectric conversion layer, add up to and contain 90 quality % more than.Preferably, more than this element total contains 95 quality %, more than more preferably containing 98 quality %.
The concrete example of the element using for the main component as thermoelectric conversion layer, can enumerate Zn (fusing point: 419 DEG C), Sb (fusing point: 630 DEG C), Co (fusing point: 1495 DEG C), Mn (fusing point: 1244 DEG C), Si (fusing point: 1410 DEG C), Mg (fusing point: 650 DEG C), Ge (fusing point: 938 DEG C), Fe (fusing point: 1538 DEG C) etc.Thermoelectric conversion layer of the present invention is preferably using the two or more alloys that form by these elements as main component.As the concrete example of preferred alloy, can enumerate Zn
4sb
3, CoSb
3, MnSi
1.
75, Mg
2si, SiGe and FeSi
2.
In addition, be that 300 DEG C of above elements preferably do not contain in fact tellurium (Te (fusing point: 449 DEG C)) as main component or other composition described later as the thermoelectric conversion layer of main component using fusing point.Tellurium has sublimability, if thereby in conversion layer, comprise tellurium layer composition can change along with the time, therefore not preferred.Specifically, the content of tellurium is preferably below 10 quality % in thermoelectric conversion layer.
[other composition]
Except above-mentioned main component, thermoelectric conversion layer can also contain dopant etc.
In the situation that containing dopant, dopant can be the kind of 300 DEG C of above elements and suitable selection according to the inorganic oxide semiconductor as main component or fusing point.
The content of other composition is preferably below 10 quality % in thermoelectric conversion layer.
In addition, in thermoelectric conversion layer using fusing point during as more than 300 DEG C elements as main component, in thermoelectric conversion layer, can also comprise fusing point and be less than the element of 300 DEG C as other composition, but consider from viewpoints such as conductivity as mentioned above, preferably the content of this element is few, in thermoelectric conversion layer, be preferably below 10 quality %, more preferably below 5 quality %.
[formation of thermoelectric conversion layer]
Thermoelectric conversion layer is by the Porous anodic oxide coating at aluminium, using inorganic oxide semiconductor or fusing point, the thermo-electric converting material film forming as more than 300 DEG C elements as main component forms (Fig. 1) by above-mentioned.As mentioned above, the porous layer of anodic oxide coating has multiple micropores, by thermo-electric converting material film forming, can in thermoelectric conversion layer, form the gap structure same with the pore structure of Porous (Fig. 3) by thereon.
The film forming of thermoelectric conversion layer preferably utilizes vapor coating method to carry out.Below, the formation method of the thermoelectric conversion layer of utilizing vapor coating method is described.
Be not particularly limited as vapor coating method, as long as the raw material that is used to form thermoelectric conversion layer being stacked on substrate and can be by the method for thermoelectricity conversion film film forming, wherein this thermoelectric conversion layer contains inorganic oxide semiconductor or fusing point is that 300 DEG C of above elements are as main component.For example can suitable employing pulsed laser deposition, the physical vapor deposition such as sputtering method, vacuum vapour deposition, electron beam evaporation plating method, ion plating method, plasmaassisted vapour deposition method, ion assisted deposition method, reactive vapour deposition method, laser ablation method, aerosol deposition method; The chemical vapour deposition techniques such as hot CVD method, catalytic chemical vapor deposition technique, plasma CVD method, organic metal vapour deposition process.Among these methods, preferably sputtering method, ion plating method.
More than the thickness of the thermoelectric conversion layer forming is preferably 50nm, more preferably more than 200nm.If thickness is thin, be difficult to provide temperature difference, and resistance in film increases, therefore not preferred.
(1) film forming of the thermoelectric conversion layer using inorganic oxide semiconductor as main component
Contain the raw material (hereinafter referred to " raw material ") of inorganic oxide semiconductor as the thermoelectric conversion layer of main component as being used to form, thereby as long as can being not particularly limited to use by utilizing vapor coating method to be vaporized and to be deposited in formation inorganic oxide on substrate.For example, can use and comprise as the metal of the Constitution Elements of the inorganic oxide of target or non-metal simple-substance, oxide, various compound (carbonate etc.) etc.In addition, also can use their mixture.In the situation that thermoelectric conversion layer comprises inorganic elements of more than two kinds, from the viewpoint of processing easiness, preferably the material that comprises each element is pre-mixed the material forming by use.
Substrate uses the substrate of the Porous anodic oxide coating with above-mentioned aluminium.
These raw materials can mix in the mode of the ratio of components that reaches target inorganic oxide, then directly use, and particularly preferably these raw materials are mixed and burn till rear use.By making burned material, in the time of vapor coating, process and become easy.
Firing condition to raw material is not particularly limited, can under the high temperature of crystallization that forms inorganic oxide, burn till, or, also can form not generating the crystallization of inorganic oxide at the lower temperature of accurate degree of burning body (Provisional baked body) and burn till.The means of burning till are not particularly limited, can adopt the means arbitrarily such as electric furnace, gas heating stove.Firing atmosphere is generally in Oxygen Flow, in the medium oxidizing atmosphere of air, can also in inert atmosphere, burn till.
Using inorganic oxide semiconductor as main component in the situation that, utilize the film forming of the thermoelectric conversion layer of vapor coating at room temperature to carry out, also can heated substrates and carry out.
(2) film forming of the thermoelectric conversion layer using fusing point as more than 300 DEG C elements as main component
As being used to form, to contain fusing point be the raw materials (hereinafter referred to " raw material ") of 300 DEG C of above elements as the thermoelectric conversion layer of main component, thereby as long as can being not particularly limited use by utilizing vapor coating method to be vaporized and to be deposited in the thermoelectricity conversion film forming using above-mentioned fusing point as more than 300 DEG C elements as main component on substrate.For example, can use the metal using above-mentioned fusing point as more than 300 DEG C elements as composition.In the situation that main component is made up of element of more than two kinds, also can use the mixture of the raw material that comprises these compositions.
Substrate uses the substrate of the Porous anodic oxide coating with above-mentioned aluminium.
These raw materials can mix in the mode of the metal ingredient ratio that reaches target alloy, then directly use, and particularly preferably these raw materials are mixed and burn till rear use.By making burned material, in the time of vapor coating, process and become easy.
In the case of using fusing point be more than 300 DEG C element as main component, utilize the film forming of the thermoelectric conversion layer of vapor coating at room temperature to carry out, also can be by base plate heating to 150 DEG C～350 DEG C of left and right and carry out.But, pile up at heated substrates not and film forming in the situation that, the degree of crystallization of composition is very low, sometimes cannot bring into play good thermoelectricity conversion performance, therefore need to after film forming, carry out annealing in process described later.The in the situation that of accumulation at heated substrates, this composition state with crystallization on substrate generates, and therefore can not carry out annealing in process, also can carry out in the lump.Carry out annealing in process by heated substrates or after film forming, the crystallization of composition advances and can bring into play good thermoelectricity conversion performance.
In the time of the thermoelectric conversion layer forming using fusing point as more than 300 DEG C elements as main component, in order to improve thermoelectricity conversion performance, the processing (crystallization processing) of carrying out the crystallization of composition is necessary.It is that high temperature carries out film forming or undertaken by the annealing in process after film forming by making substrate temperature that crystallization is processed.In the time using low-melting element as the main component of thermoelectric conversion layer, it is processed and melting by this crystallization, and the gap structure in conversion layer disappears.In the present invention, be the main components of 300 DEG C of above elements as conversion layer by using fusing point, can maintain the gap structure of conversion layer and reduce conductive coefficient, and can improve thermoelectricity conversion performance by sufficient crystallization.
In addition, there is the substrate of the Porous anodic oxide coating of aluminium by use, can obtain the element of the adaptation excellence of substrate and thermoelectric conversion layer.Adaptation by substrate and thermoelectric conversion layer improves, and can suppress the warpage of substrate or peel off the crackle causing, and can bring into play good thermoelectricity conversion performance.
Annealing in process temperature is preferably 350 DEG C～500 DEG C left and right.By carrying out annealing in process in this temperature range, the crystallization of thermoelectricity conversion film advances, and has good thermoelectricity conversion performance.In the time that annealing in process temperature is too low, crystallization cannot fully carry out, and thermoelectricity conversion performance variation, therefore not preferred.On the other hand, if annealing in process excess Temperature there will be other phase, thermoelectricity conversion performance still can reduce, therefore not preferred.
Atmosphere when annealing in process is preferably inert gas atmosphere.As inert gas, can use argon gas, helium, nitrogen.In the time that the reduction of thermoelectricity conversion film is carried out in hope, can use argon gas/hydrogen or nitrogen/hydrogen etc.Pressure is now not particularly limited, and can be any one in decompression, atmospheric pressure, pressurization.
The annealing in process time is different because of size, the thickness etc. of thermoelectricity conversion film, as long as till the crystallization that processing is proceeded to thermoelectricity conversion film fully carries out, be generally about 10 minutes to 12 hours, is preferably the processing time of 1 hour to 4 hours.
Thermoelectric conversion element of the present invention can be suitable for hot spring generating, power supply for wrist-watch, semiconductor driving power, for Miniature Sensor in the purposes such as power supply, solar power generation, waste-heat power generation.
Embodiment
, illustrate in greater detail the present invention by embodiment below, but the present invention is not limited to these embodiment.
The manufacture (treatment fluid: sulfuric acid) of Production Example 1 anodic oxidation aluminium base
(A) pre-treatment (electrolytic polishing processing)
With the square area cutting raffinal substrate (manufacture of Sumitomo light metal society, purity 99.99 quality %, thickness 0.4mm) of 10cm, thereby can carry out anodized, use the electrolytic polishing liquid of following composition, under the condition of voltage 25V, 65 DEG C of fluid temperatures, flow rate of liquid 3.0m/min, implement electrolytic polishing processing.
Negative electrode is carbon electrode, and power supply uses GP0110-30R (STOL is made society of institute and manufactured).In addition, the flow velocity of electrolyte uses eddy current type flow monitoring instrument FLM22-10PCW (AS ONE manufacture) to carry out instrumentation.
(electrolytic polishing liquid composition)
85 quality % phosphoric acid (manufacturing reagent with Guang Chun medicine society) 660mL
Pure water 160mL
Sulfuric acid 150mL
Ethylene glycol 30mL
(B) anodized operation
Then, for electrolytic polishing aluminium base after treatment, utilize the electrolyte of 0.30mol/L sulfuric acid, under the condition of voltage 25V, 15 DEG C of fluid temperatures, flow rate of liquid 3.0m/min, implement the anodized of 5 hours.
Afterwards, the demoulding processing of 12 hours is flooded the aluminium base after anodized in enforcement in the mixed aqueous solution (liquid temperature: 50 DEG C) of 0.2mol/L anhydrous chromic acid and 0.6mol/L phosphoric acid.
Afterwards, utilize the electrolyte of 0.30mol/L sulfuric acid, under the condition of voltage 25V, 15 DEG C of fluid temperatures, flow rate of liquid 3.0m/min, implement the anodized again of 3 hours.
It should be noted that, in anodized and again anodized, negative electrode is stainless steel electrode, and power supply all uses GP0110-30R (STOL is made society of institute and manufactured).In addition, cooling device uses NeoCool BD36 (large and science society manufactures), and agitating heater uses pair stirrer PS-100 (manufacture of EYELA society).In addition, the flow velocity of electrolyte uses eddy current type flow monitoring instrument FLM22-10PCW (AS ONE manufacture) to carry out instrumentation.
For the porous structure of obtained anodic oxidation aluminium base, utilize respectively following method measurement and calculation to go out average pore size φ, average span P, aperture opening ratio (φ/P).
Use electron microscope to take anodised aluminium surface.From photographic images, select 20 peristomes, and instrumentation diameter, obtain average pore size φ.In addition, the distance between centers of 2 peristomes of instrumentation, calculates average span P and aperture opening ratio (φ/P).
The manufacture (treatment fluid: oxalic acid) of Production Example 2 anodic oxidation aluminium bases
(A) pretreatment procedure (electrolytic polishing processing)
(A) same carrying out with Production Example 1.
(B) anodic oxide coating forms operation (anodized)
For electrolytic polishing obtained above aluminium base after treatment, utilize the electrolyte of 0.50mol/L oxalic acid, under the condition of voltage 40V, 15 DEG C of fluid temperatures, flow rate of liquid 3.0m/min, implement 1 hour anodized.And then for the sample after anodized, utilize 0.5mol/L phosphate aqueous solution under the condition of 40 DEG C, to flood 25 minutes, implement demoulding processing.
Repeat after four these processing with this order, utilize the electrolyte of 0.50mol/L oxalic acid, under the condition of voltage 40V, 15 DEG C of fluid temperatures, flow rate of liquid 3.0m/min, implement 4 hours anodized again, and then utilize 0.5mol/L phosphate aqueous solution under the condition of 40 DEG C, to flood 25 minutes, implement demoulding processing, having formed thus micropore on aluminium base surface is straight tube-like and the anodic oxide coating with honeycomb arrangement.
It should be noted that, in anodized and again anodized, negative electrode is stainless steel electrode, and power supply all uses GP0110-30R (STOL is made society of institute and manufactured).In addition, as cooling device, use NeoCoolBD36 (large and science society manufactures), as agitating heater, use pair stirrer PS-100 (manufacture of EYELA society).The flow velocity of electrolyte uses eddy current type flow monitoring instrument FLM22-10PCW (AS ONE manufacture) to carry out instrumentation.
For the porous structure of obtained anodic oxidation aluminium base, with Production Example 1 similarly respectively measurement and calculation go out average pore size φ, average span P, aperture opening ratio (φ/P).
The making of embodiment 1-1 thermoelectric conversion element
Use the anodic oxidation aluminium base that utilizes sulfuric acid treatment obtaining in Production Example 1, by thermoelectric conversion layer film forming, make thermoelectric conversion element by sputtering method.
Make by In
2o
3: 90%-SnO
2: the target that 10% (ITO, purity: 4N) forms, uses magnetic control sputtering device to carry out film forming.The thickness of thermoelectric conversion layer is now 150nm.
The performance of the thermoelectric conversion layer forming by following manner evaluation.The results are shown in table 1.
Embodiment 1-2
Substrate is changed to the anodic oxidation aluminium base that utilizes oxalic acid treatment obtaining in Production Example 2, in addition with embodiment 1-1 similarly on substrate by thermoelectric conversion layer film forming, and evaluated performance.The results are shown in table 1.
Embodiment 1-3
Use the anodic oxidation aluminium base that utilizes oxalic acid treatment obtaining in Production Example 2, by thermoelectric conversion layer film forming, make thermoelectric conversion element by sputtering method.
Make by In
2o
3: the target that 90%-ZnO:10% (IZO) forms, uses magnetic control sputtering device to carry out film forming.The thickness of thermoelectric conversion layer is now 200nm.
Similarly evaluate the performance of formed thermoelectric conversion layer with embodiment 1-1.The results are shown in table 1.
Comparative example 1-1
Except substrate is changed to quartz base plate, with embodiment 1-1 similarly on substrate by thermoelectric conversion layer film forming, and evaluated performance.The results are shown in table 1.
[mensuration of pyroelecthc properties]
Use pyroelecthc properties determinator model RZ2001i (OZAWA SCIENCE society goods name), in temperature is the air atmosphere of 100 degree, measure, measured Seebeck coefficient (V/k) and conductivity (S/m).
[mensuration of conductive coefficient]
In thermoelectric conversion layer by the reflector being formed by molybdenum (thickness 100nm) film forming, use film thermal instrument for measuring of physical property PicoTR (PicoTherm Corporation goods name), measured conductive coefficient (W/ (m k)) by surface heating/surface temperature measurement method.
[evaluation of thermoelectricity capability factor Z]
According to following formula (A), calculate performance factor Z by the above-mentioned Seebeck coefficient calculating, conductivity and conductive coefficient.
Formula (A): Z={ (Seebeck coefficient)
2× (conductivity) }/(conductive coefficient)
[evaluation of gap structure]
Use scanning type probe microscope Nanopics1000 (SII NanoTechnology Inc. Co., Ltd.), observe the surface of thermoelectric conversion layer by rapping pattern.Field range is made as to 1000nm, by having or not of the concavo-convex confirmation space on surface.
[table 1]
Table 1
As shown in Table 1, in embodiment 1-1～1-3, thermoelectric conversion layer has gap structure, and conductive coefficient is low, and the absolute value of Seebeck coefficient is also large, demonstrates excellent thermoelectricity capability.Particularly, in the embodiment 1-2 that has used the substrate that utilizes oxalic acid treatment, the absolute value of Seebeck coefficient significantly improves.On the other hand, in the comparative example 1-1 that has used quartz base plate, thermoelectricity capability does not have embodiment 1-1～1-3 large.
The making of embodiment 2-1 thermoelectric conversion element
Use the anodic oxidation aluminium base that utilizes sulfuric acid treatment obtaining in Production Example 1, by thermoelectric conversion layer film forming, make thermoelectric conversion element by sputtering method.
Make by Zn
4sb
3the target that (zinc antimony) forms, uses magnetic control sputtering device, and the temperature of substrate is maintained to 150 DEG C of one side carries out film forming on one side.The thickness of thermoelectric conversion layer is now 200nm.In addition, use the electric furnace that has carried out displacement by argon gas, carry out 4 hours annealing in process at 350 DEG C, formed thermoelectric conversion layer.
Evaluate the performance of thermoelectric conversion layer by following manner.The results are shown in table 2-1.
Embodiment 2-2
Except substrate being changed to the anodic oxidation aluminium base that utilizes oxalic acid treatment obtaining in Production Example 2, with embodiment 2-1 similarly on substrate by thermoelectric conversion layer film forming, and evaluated performance.The results are shown in table 2-1.
Comparative example 2-1
Except substrate is changed to quartz base plate, with embodiment 2-1 similarly on substrate by thermoelectric conversion layer film forming, and evaluated performance.The results are shown in table 2-1.
Comparative example 2-2～2-3
As thermo-electric converting material, replace Zn
4sb
3and use the each material of table shown in 2-2, and the temperature and time of annealing in process is changed to the condition shown in table 2-2, in addition with embodiment 2-2 similarly on substrate by thermoelectric conversion layer film forming, and evaluated performance.The results are shown in table 2-2.It should be noted that, the fusing point of Bi is 271 DEG C.
[evaluation of thermoelectricity capability]
Use pyroelecthc properties determinator model RZ2001i (goods name, OZAWA SCIENCE society manufacture), in temperature is the air atmosphere of 100 degree, measure, measured thermo-electromotive force (Seebeck coefficient: V/k) and conductivity (S/m).According to following formula, calculate power factor (PF) by obtained Seebeck coefficient and conductivity meter.
PF=(Seebeck coefficient)
2× (conductivity)
[evaluation of gap structure]
Use scanning type probe microscope Nanopics1000 (SII NanoTechnology Inc. Co., Ltd.), observe the surface of thermoelectric conversion layer by rapping pattern.Field range is made as to 1000nm, by having or not of the concavo-convex confirmation space on surface.
[adaptation evaluation]
Utilizing cellophane tape to carry out belt stripping test, is zero by the average evaluation of peeling off without thermoelectric conversion layer from substrate, by have the average evaluation peeled off for ×.
[table 2-1]
Table 2-1
* power factor (power factor): μ W/ (mK
2) (mensuration temperature: 100 DEG C)
[table 2-2]
Table 2-2
From table 2-1 and 2-2, having used in embodiment 2-1, the 2-2 of anodic oxidation aluminium base, form gap structure in thermoelectric conversion layer inside.On the other hand, in the comparative example 2-1 that has used quartz base plate, do not form gap structure.In addition, embodiment 2-1,2-2 demonstrate excellent thermoelectricity capability, also good with the adaptation of substrate.In the comparative example 2-1 that has used quartz base plate, even if carry out annealing in process, thermoelectricity capability does not have embodiment 2-1,2-2 large yet.
Using low-melting element to form in the comparative example 2-2～2-3 of thermoelectric conversion layer, do not confirm the gap structure of conversion layer yet.Think that this is the melting because of low-melting first procatarxis annealing in process, the gap structure of conversion layer disappears.In addition, in comparative example 2-3, metallic luster disappears compared with before annealing in process, and the ratio of thermoelectric conversion layer is anti-infinitely increases greatly.Think that this is because distillation has occurred the tellurium that conversion layer comprises.
Embodiment 2-3
Use the anodic oxidation aluminium base that utilizes oxalic acid treatment obtaining in Production Example 2, by thermoelectric conversion layer film forming, make thermoelectric conversion element by sputtering method.
Make by CoSb
3the target that (cobalt antimony) forms, uses magnetic control sputtering device, and the temperature of substrate is maintained to 150 DEG C of one side carries out film forming on one side.The thickness of thermoelectric conversion layer is now 200nm.In addition, use the electric furnace that has carried out displacement by argon gas, carry out 2 hours annealing in process at 350 DEG C, form thermoelectric conversion layer, and evaluated performance.
The results are shown in table 2-3.
Embodiment 2-4
Use the anodic oxidation aluminium base that utilizes oxalic acid treatment obtaining in Production Example 2, by thermoelectric conversion layer film forming, make thermoelectric conversion element by sputtering method.
Make by MnSi
1.75the target that (silication manganese) forms, uses magnetic control sputtering device, and the temperature of substrate is maintained to 150 DEG C of one side carries out film forming on one side.The thickness of thermoelectric conversion layer is now 200nm.In addition, use the electric furnace that has carried out displacement by argon gas, carry out 2 hours annealing in process at 350 DEG C, form thermoelectric conversion layer, and evaluated performance.
The results are shown in table 2-3.
Embodiment 2-5
Use the anodic oxidation aluminium base that utilizes oxalic acid treatment obtaining in Production Example 2, by thermoelectric conversion layer film forming, make thermoelectric conversion element by sputtering method.
Make by FeSi
2the target that (iron suicide) forms, uses magnetic control sputtering device, and the temperature of substrate is maintained to 150 DEG C of one side carries out film forming on one side.The thickness of thermoelectric conversion layer is now 200nm.In addition, use the electric furnace that has carried out displacement by argon gas, carry out 2 hours annealing in process at 350 DEG C, form thermoelectric conversion layer, and evaluated performance.
The results are shown in table 2-3.
Comparative example 2-4
Use quartz glass except replacing anodic oxidation aluminium base, similarly make thermoelectric conversion element with embodiment 2-3, and evaluated performance.The results are shown in table 2-3.
[table 2-3]
Table 2-3
* power factor (power factor): μ W/ (mK
2) (mensuration temperature: 100 DEG C)
From table 2-3, use the embodiment 2-3～2-5 of anodic oxidation aluminium base to form gap structure in thermoelectric conversion layer inside, also good with the adaptation of substrate.In addition, thermoelectricity conversion performance is also than thermo-electric converting material Zn
4sb
3(table 2-1) is low, but demonstrates good thermoelectricity conversion performance.
On the other hand, in the comparative example 2-4 that has used quartz base plate, do not form gap structure, also poor with the adaptation of substrate.In addition, thermoelectricity conversion performance is also low than embodiment 3.
Although describe the present invention in conjunction with above-mentioned execution mode, but applicant's intention be as long as no special declaration the present invention at all circumscribeds not of any details place of explanation, think and should not violate the invention spirit and scope shown in claims and broadly explain.
The application requires the priority of the patent application Japanese Patent Application 2011-229554 submitting in Japan on October 19th, 2011 and the patent application Japanese Patent Application 2011-229555 submitting in Japan on October 19th, 2011, and its content is introduced as a part for the record content of this specification using the form of reference.
Symbol description
1: thermoelectric conversion element
2: aluminium base
3,13,23: anodic oxide coating
4: thermoelectric conversion layer
15,25: micropore
26: thermo-electric converting material
Claims (12)
1. a thermoelectric conversion element, on substrate upper strata, long-pending thermoelectric conversion layer forms for it, described substrate has the Porous anodic oxide coating of aluminium, and it is that 300 DEG C of above elements are as main component and have gap structure that described thermoelectric conversion layer contains inorganic oxide semiconductor or fusing point.
2. thermoelectric conversion element as claimed in claim 1, wherein, described inorganic oxide semiconductor contains indium.
3. thermoelectric conversion element as claimed in claim 1, wherein, described inorganic oxide semiconductor is for selecting free n
2o
3, SnO
2, ZnO, SrTiO
3, WO
3, MoO
3, In
2o
3-SnO
2, fluorine-doped tin oxide, antimony-doped tin oxide, stibium-doped zinc oxide, Ga-doped zinc oxide, In
2o
3-ZnO and gallium doping In
2o
3material in the group of-ZnO composition.
4. thermoelectric conversion element as claimed in claim 1, wherein, it is that 330 DEG C of above elements are as main component that described thermoelectric conversion layer contains fusing point.
5. the thermoelectric conversion element as described in claim 1 or 4, wherein, described thermoelectric conversion layer contains selects free Zn
4sb
3, CoSb
3, MnSi
1.
75, Mg
2si, SiGe and FeSi
2alloy in the group of composition is as main component.
6. the thermoelectric conversion element as described in any one in claim 1～5, wherein, the aperture opening ratio of described Porous anodic oxide coating meets following mathematical expression (I),
Mathematical expression (I) aperture opening ratio=φ/P>0.5
In formula, φ represents average pore size, and P represents average span.
7. the thermoelectric conversion element as described in any one in claim 1～6, wherein, the average pore size in the hole of described Porous anodic oxide coating is more than 60nm.
8. the manufacture method of a thermoelectric conversion element, described manufacture method comprises following operation: on substrate, thermo-electric converting material film forming is formed to thermoelectric conversion layer, described substrate has the Porous anodic oxide coating of aluminium, and described thermo-electric converting material contains inorganic oxide semiconductor or fusing point is that 300 DEG C of above elements are as main component.
9. the manufacture method of thermoelectric conversion element as claimed in claim 8, wherein, described manufacture method comprises following operation: on substrate, thermo-electric converting material film forming is formed to thermoelectric conversion layer, described substrate has the Porous anodic oxide coating of aluminium, and it is that 300 DEG C of above elements are as main component that described thermo-electric converting material contains fusing point; And this thermoelectric conversion layer is carried out to annealing in process.
10. the manufacture method of thermoelectric conversion element as claimed in claim 8, wherein, described manufacture method comprises following operation: on substrate, be, under more than 150 DEG C conditions, thermo-electric converting material film forming is formed to thermoelectric conversion layer at substrate temperature, described substrate has the Porous anodic oxide coating of aluminium, and it is that 300 DEG C of above elements are as main component that described thermo-electric converting material contains fusing point.
The manufacture method of 11. thermoelectric conversion elements as described in any one in claim 8～10, wherein, described manufacture method comprises following operation: aluminium sheet is carried out to anodic oxidation with oxalic acid, obtain having the substrate of described Porous anodic oxide coating.
The manufacture method of 12. thermoelectric conversion elements as described in any one in claim 8～11, wherein, described film forming is undertaken by vapor coating method.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-229555 | 2011-10-19 | ||
| JP2011229555 | 2011-10-19 | ||
| JP2011229554 | 2011-10-19 | ||
| JP2011-229554 | 2011-10-19 | ||
| PCT/JP2012/076971 WO2013058327A1 (en) | 2011-10-19 | 2012-10-18 | Thermoelectric conversion element and process for producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103890986A true CN103890986A (en) | 2014-06-25 |
Family
ID=48140970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280051044.6A Pending CN103890986A (en) | 2011-10-19 | 2012-10-18 | Thermoelectric conversion element and process for producing same |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20140224297A1 (en) |
| CN (1) | CN103890986A (en) |
| WO (1) | WO2013058327A1 (en) |
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| CN109503147A (en) * | 2018-12-14 | 2019-03-22 | 昆明理工大学 | A kind of Ga element doping In2O3(ZnO)3Thermoelectric material and the preparation method and application thereof |
| CN109755377A (en) * | 2018-12-17 | 2019-05-14 | 新奥科技发展有限公司 | A kind of skutterudite-base thermoelectrical material and preparation method thereof |
| CN110014718A (en) * | 2019-04-28 | 2019-07-16 | 大连海事大学 | A method of gallium base thermal interface material applications are enhanced into interface heat transfer in aluminium substrate |
| CN112479683A (en) * | 2020-12-17 | 2021-03-12 | 中山智隆新材料科技有限公司 | Preparation method of doped IGZO material |
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|---|---|---|---|---|
| WO2015022935A1 (en) * | 2013-08-14 | 2015-02-19 | 三菱レイヨン株式会社 | Method for producing cylindrical nanoimprinting mold and method for producing nanoimprinting reproduction mold |
| CN105355771B (en) * | 2015-10-16 | 2018-09-28 | 中国科学院上海硅酸盐研究所 | A kind of high power factor zinc oxide thermoelectric material and preparation method thereof |
| KR102652258B1 (en) * | 2016-07-12 | 2024-03-28 | 에이비엠 주식회사 | Metal component and manufacturing method thereof and process chamber having the metal component |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109503147A (en) * | 2018-12-14 | 2019-03-22 | 昆明理工大学 | A kind of Ga element doping In2O3(ZnO)3Thermoelectric material and the preparation method and application thereof |
| CN109503147B (en) * | 2018-12-14 | 2021-09-10 | 昆明理工大学 | Ga element doped In2O3(ZnO)3Thermoelectric material and preparation method and application thereof |
| CN109755377A (en) * | 2018-12-17 | 2019-05-14 | 新奥科技发展有限公司 | A kind of skutterudite-base thermoelectrical material and preparation method thereof |
| CN110014718A (en) * | 2019-04-28 | 2019-07-16 | 大连海事大学 | A method of gallium base thermal interface material applications are enhanced into interface heat transfer in aluminium substrate |
| CN110014718B (en) * | 2019-04-28 | 2021-05-18 | 大连海事大学 | Method for applying gallium-based thermal interface material to aluminum substrate to enhance interface heat transfer |
| CN112479683A (en) * | 2020-12-17 | 2021-03-12 | 中山智隆新材料科技有限公司 | Preparation method of doped IGZO material |
Also Published As
| Publication number | Publication date |
|---|---|
| US20140224297A1 (en) | 2014-08-14 |
| WO2013058327A1 (en) | 2013-04-25 |
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